1. Field of the Invention
The present invention relates to a method and an apparatus for analyzing an organic macromolecular component in a solution based on a flow analysis method and to applications thereof. In particular, the present invention relates to an analytical method and an apparatus suitable for quantitatively analyzing very small amounts of glues or gelatins contained in metallic electrolytic solutions, such as copper electrolytic solutions and plating solutions.
2. Description of the Related Art
Various additives are added to electrolytic solutions and plating solutions in accordance with various purposes of improving brightness and smoothness of electrodeposited metal surfaces, hardening plated layers, etc. As the additive, in general, glues are used in electrolytic smelting and gelatins are used in plating. Herein, it is very important in quality control to keep concentrations thereof within specified ranges. For example, although glues are used for improving smoothness of electrodeposited surfaces, when concentrations thereof are too high, polarization is increased to a great degree so that there are problems of deposition of impurities, such as bismuth, contained in the electrolytic solutions, etc.
Therefore, a method for analyzing proteins, such as glues or gelatins, contained in solutions with a high degree of precision has been required. Most of conventional methods for analyzing proteins are performed under from weakly acidic to weakly basic conditions, and there are few analytical methods which can be applied under strongly acidic conditions of pH 1 or less, as in electrolytic solutions, plating solutions, etc. Hitherto, proteins, such as glues or gelatins, contained in electrolytic solutions, plating solutions, etc., have been measured by potentiometric titration, Kjeldahl method, etc., although specific apparatuses and complicated operations have been required in those cases. In the Kjeldahl method, glues are measured after being decomposed into nitrogen in a state of ammonia, although in many cases, nitrogen compounds other than proteins are contained in the electrolytic solutions so as to make precise measurements difficult.
In addition, as a quantitative method for analyzing gelatins and glues in the strongly acidic solution, a method in which those are collected on membrane filters, are bonded with a specific reagent (Amide Black 10B coloring matter), and after excess coloring matters are washed out, the coloring matters are eluted so as to determine gelatins, etc., (Japanese Unexamined Patent Application Publication No. 2-69660), a method in which after gelatins, etc., have been collected on a filter, the resulting filter is dried so as to determine gelatins, etc., based on reflectance (Japanese Unexamined Patent Application Publication No. 6-337247), etc., are reported. Regarding these methods, there are, however, problems that an amount of collected glues is much affected by pore diameters of the filter so as to increase measurement errors, a filtering apparatus for collecting with the filter is required and operations are complicated, and the analytical cost is increased due to disposable filters.
The present invention has solved the aforementioned problems in conventional analytical methods. It is an object of the present invention to provide a flow analysis method and an apparatus, thereby organic macromolecular components, such as glues and gelatins, in a solution can be promptly and precisely determined even in a strongly acidic solution.
The present invention is due to the completion of a system for measurement with a high degree of reliability and with ease of handling, in which operations of separating organic macromolecular components in a solution by adsorption on a resin, leading these to a gel permeation chromatograph, and analyzing are performed based on the flow analysis.
That is, the present invention relates to the following flow analysis method for separating and analyzing an organic macromolecular component in a sample.
(1) A method for analyzing an organic macromolecular component based on a flow analysis method with a measuring system including a sample introducing section, a preparing section, and a measuring section, composed of steps of supplying a sample with a carrier solution into the measuring system through the introducing section, leading the sample to the preparing section and separating an organic macromolecular component in the sample, and leading the separated organic macromolecular component to the measuring section and analyzing. Herein, the step of separating the organic macromolecular component includes steps of the organic macromolecular component in the sample being adsorbed on a resin and introducing an eluant into the preparing section and eluting the organic macromolecular component adsorbed on the resin.
(2) A method of analysis according to the aforementioned method (1), further composed of the steps of supplying the sample into the measurement system through the introducing section while a pipeline for feeding the sample from the introducing section to the preparing section and a pipeline for discharging a solution from the preparing section out of the measurement system are communicated with the preparing section, leading the sample to the preparing section, the organic macromolecular component in the sample being adsorbed on the resin in the preparing section while leading the solution discharged from the preparing section out of the measurement system, switching pipelines communicating with the preparing section so that a pipeline for supplying the eluant and a pipeline connected to the measuring section communicate with the preparing section, introducing the eluant into the preparing section so as to elute the organic macromolecular component adsorbed on the resin, and leading the resulting solution containing the organic macromolecular component to the measuring section and analyzing.
(3) A method of analysis according to the aforementioned method (1), in which the eluant is used after a buffer solution for preventing the organic macromolecular components from coagulating is added thereto or the buffer solution is added to the solution containing the organic macromolecular component between the preparing section and the measuring section.
(4) A method of analysis according to the aforementioned method (1) or (2), in which gel permeation chromatography is used as an analyzing device so as to fractionate and analyze the organic macromolecular component separated from the sample.
(5) A method of analysis according to the aforementioned method (1) or (2), in which an amount of glues or gelatins separated from the sample or an amount of decomposition products thereof is measured.
(6) A method of analysis according to the aforementioned method (1) or (2), in which gel permeation chromatography is used as an analyzing device so as to fractionate glues or gelatins separated from the sample and to measure the amount thereof or an amount of decomposition products thereof.
(7) A method of analysis according to the aforementioned method (1) or (2), in which an acid-proof and hydrophobic adsorption resin is used as a resin for adsorbing the organic macromolecular component in the sample.
(8) A method of analysis according to the aforementioned method (1) or (2), in which an electrolytic solution taken from a step of metallic electrolysis or a plating solution taken from a step of plating is used as a sample solution.
(9) A method for controlling a step of metallic electrolysis with a method of analysis according to the aforementioned method (1) or (2), in which the method of analysis is further composed of steps of taking a sample solution from an electrolytic solution in the step of metallic electrolysis, measuring an amount of glues or gelatins separated from the sample of the electrolytic solution or an amount of decomposition products thereof, and feeding back the analytical results of the measurement to the step of metallic electrolysis.
(10) A method for controlling a step of plating with a method of analysis according to the aforementioned method (1) or (2), in which the method of analysis is further composed of steps of taking a sample solution from a plating solution in the step of plating, measuring an amount of glues or gelatins separated from the sample of plating solution or an amount of decomposition products thereof, and feeding back the analytical results of the measurement to the step of plating.
In the method of analysis according to the present invention, as described above, a series of operations of separating proteins and organic macromolecular components such as glues and gelatins contained in the solution by adsorption on the resin, leading these to a gel permeation chromatograph, and analyzing are performed based on the flow analysis method. Since operations of the introduction of the sample to the analysis of the organic macromolecular component can be continuously performed in a short time, the analytical results can be promptly obtained. Therefore, regarding the organic macromolecular component, behaviors during decomposition and intermediate products can be grasped. Since separation is performed using the hydrophobic adsorption resin and analysis is performed using the gel permeation chromatography, the organic macromolecular component can be analyzed independent of the molecular weight. Furthermore, when the organic macromolecular components are fed to the measuring section, a buffer solution for preventing the coagulation thereof may be added so as not to cause a blockage of pipeline, etc., and therefore, the analysis can be performed with a high degree of reliability. This buffer solution may be blended beforehand to the eluant or may be added between the preparing section and the measuring section. When the buffer solution is added after the organic macromolecular components adsorbed on the resin are eluted, an effect of eluting is improved and an effect of preventing the organic macromolecular components from coagulating is also improved.
The flow analysis method according to the present invention can be applied to strongly acidic solutions, such as metallic electrolytic solutions and plating solutions, by using an acid-proof and hydrophobic adsorption resin as the resin for adsorbing the organic macromolecular components. Therefore, the quantitative analysis of glues contained in electrolytic solutions of copper electrolytic smelting, etc., can be easily performed so that it can be used as a method for controlling electrolytic operations. According to the method of analysis of the present invention, since a continuous automatic analysis is possible instead of a conventional batch method for controlling electrolysis by the manual work, accurate operation control of the electrolytic smelting for long time is possible.
The present invention further relates to the following apparatuses for flow analysis.
(11) An apparatus for flow analysis of an organic macromolecular component composed of a sample introducing section, a preparing section, and a measuring section integrally connected by pipelines, in which the preparing section is provided with an adsorbing device for the organic macromolecular component and an eluting device for the organic macromolecular component as separating devices for the organic macromolecular component in the sample, and the measuring section is provided with a fractionating and analyzing device for the separated organic macromolecular component.
(12) An apparatus for flow analysis according to the aforementioned apparatus for analysis (11), further provided with a column filled with a resin for adsorbing the organic macromolecular component in the sample, and a pipeline for introduction from the introducing section out of the measurement system and a pipeline for elution from a supply source of the eluant to the measuring section each connected to the column so as to be freely switched to each other, the adsorbing device and the eluting device for the organic macromolecular component being composed thereof.
(13) An apparatus for flow analysis according to the aforementioned apparatus for analysis (11) or (12), further provided with a buffering section for addition of a buffer solution for preventing organic macromolecular components from coagulating between the preparing section and the measuring section.
(14) An apparatus for flow analysis according to the aforementioned apparatus for analysis (11) or (12), further provided with a gel permeation chromatograph in the measuring section as an analytical device for the organic macromolecular component.
(15) An apparatus for flow analysis according to the aforementioned apparatus for analysis (11) or (12), further provided with a thermostatic chamber in the measuring section, and further provided with a gel permeation chromatograph in the thermostatic chamber.
(16) An apparatus for flow analysis according to the aforementioned apparatus for analysis (11) or (12), further provided with a thermostatic chamber in the measuring section, and further provided with a gel permeation chromatograph including a plurality of columns with different mesh diameters of gels in the thermostatic chamber.
(17) An apparatus for flow analysis according to the aforementioned apparatus for analysis (11) or (12), further provided with an automatically controlling device for feed of solution and discharge of solution in the sample introducing section and in the preparing section, temperature adjustment in the measuring section, and actions of a detecting section so as to continuously and automatically perform operations of from sample introduction to fractionation and analysis by way of separation of the organic macromolecular component.
According to the aforementioned apparatus for flow analysis, the organic macromolecular components contained in the sample can be separated with ease of operation and can be analyzed. Furthermore, the column for adsorbing the organic macromolecular components and the pipelines for sample introduction and for leading the separated organic macromolecular component to the measuring section connected to the resin column so as to be freely switched to each other are provided. Therefore, feed of the sample to the resin column and discharge, adsorption and desorption of the organic macromolecular component by the resin, and feed of the solution to the measuring section can be mechanically and smoothly performed in a short time. By the buffering section being provided between the preparing section and the measuring section, separated organic macromolecular components are prevented from coagulating so as not to cause a blockage of the pipeline and the analysis can be performed with a high degree of reliability. By the columns with different mesh diameters of gels for gel permeation chromatography being provided in a plurality of stages in the thermostatic chamber, precise analysis can be performed according to the molecular weight of the organic macromolecular component. In the apparatus for analysis according to the present invention, since the measurement system of from the sample introducing section to the measuring section by way of the preparing section is integrally communicated by pipelines, and pipelines connected to the preparing section are formed so as to be freely switched to each other, operations of feeding solution and discharging solution in each section can be automatically controlled. Therefore, a series of operations of from introduction of the sample to analysis can be automated with the aforementioned automatically controlling device being provided.